Dibenzo-1, 2-thiazines



United States Patent 3,356,678 DIBENZfi-LZ-THIAZINES Wilhelm E. Prick,Pfefiingen, and Guido Schetty, Aesch, Switzerland, assignors to J. R.Geigy A.G., Basel, Switzerland No Drawing. Filed Mar. 25, 1966, Ser. No.537,314 Claims priority, application Switzerland, Dec. 6, I962,14,325/62 16 Claims. ((Jl. 260243) ABSTRACT OF THE DISCLOSURE There areprovided substituted 6H-dibenzo[c,e]-1,2- thiazine-5,5-dioxides of thegeneral Formula I wherein the substituent variables are as defined inthe specification. In addition, the alkali metal, alkaline earth metaland ammonium salts of the compounds falling under the above formula inwhich R is hydrogen are provided. These compounds have been found topossess excellent insecticidal and acaricidal activity. The compoundsare particularly elfective against insects in all stages of developmentwhich injure keratin fiber, such as moth larvae as well as for andcarpet beetle larvae.

This application is a continuation-in-part of our copending applicationSerial No. 328,175, filed December 5, 1963, now abandoned.

The present invention concerns processes for the pro duction of newinsecticidally and acaricidally active dibenzo-l,2-thiazine derivatives.

It has now been found that substituted 6H-dibenzo[c,e]-1,2-thiazine-5,5-dioxides of the general Formula I wherein the Rs,independently of each other, represent halogen of an atom number rangingfrom 9 to 35, or trifluoromethyl,

X represents an oxygen or sulfur atom, or an SO- or 55 SO group,

R represents lower alkyl, lower alkoxy-lower alkyl, halogeno-lower alkylwherein halogen is of an atom number ranging from 9 to 35, hydroXy-loweralkyl, phenyl, lower alkyl-phenyl, halogeno-lower alkyl-phenyl whereinhalogen is of an atom number ranging from 9 to 35, halogenophenylwherein halogen is of an atom num- Patented Dec. 5, 1967 ber rangingfrom 9 to 35, lower alkoxy-phenyl, nitrophenyl, amino-phenyl orhydroxyphenyl,

The R s, independently of each other, represent halogen of an atomnumber ranging from 9 to 35, or trifluoromethyl,

R represents hydrogen, lower alkyl, phenyl, lower alkylphenyl,halogeno-phenyl wherein halogen is of an atom number ranging from 9 to35, halogeno-lower alkylphenyl wherein halogen is of an atom numberranging 10 from 9 to 35, benzyl, lower alkyl-benzyl, halogenobenzylwherein halogen is of an atom number ranging from 9 to 35, andhalogeno-lower alkyl-benzyl wherein halogen is of an atom number rangingfrom 9 to 35, lower alkanoyl, N,N-di(lower alkyl)-amino-lower alkyl orN-lower alkyl-amino-lower alkyl, benzoyl, or halogeno-benzoyl whereinhalogen is of one of the atom numbers 9, 17 and 35,

n represents an integer ranging from 0 to l,

p represents an integer ranging from 0 to 4,

20 m represents an integer ranging from 0 to (4-n), and

q represents an integer ranging from 0 to 2, the sum of m+n+p being atleast equal to l, and the sum of p-+q being not greater than 4,

as well as the alkali metal salts, alkaline earth metal salts andammonium salts of those compounds falling under Formula I in which R ishydrogen, have surprisingly excellent insecticidal activity, inparticular against insects in all stages of development which injurekeratin fibers, such as moth larvae as well as fur and carpet beetlelarvae.

Diptera:

Culicidae Muscidae Orthoptera: Acrididae Blattidae Coleoptera:

Dermestidae Tenebrionidae 5O Chrysomelidae Bruchidae CurculionidaeLepidoptera:

Pyralididae Noctuidae Hymenoptera:

Formicidae Compounds of Formula I also serve as active ingredients inacaricidal agents, particularly against the families Tetranychidae,Argasidae and Ixodidae of the Order Acarinae.

The compounds of Formula I according to the invention are distinguishedby a pronounced activity as stomach poisons for insects devouring theleaves of plants. This is especially the case with certain divalentmetal salts of the compounds falling under Formula I, as will beexplained more in detail further below.

The compounds of the general Formula I draw from 70 aqueous dispersionsand, in the case of R being hydrogen, also from aqueous solutions oftheir salts onto keratin fibers because of their aflinity thereto and inthis waythey protect keratin material treated therewith from injury bythe larvae of moths and other small winged insects as well as frominjury by the larvae of fur and carpet beetles (Anthrenus andAttagenus).

Some of the new active ingredients are also active against termites and,in addition, some have bactericidal or bacteriostatic activity so thatthey can also be used for disinfection purposes.

Among the salts derived from compound of Formula I in which R ishydrogen and from a divalent metal, those which are chlorinated6H-dibenzo[c,e]-l,2-thiazine-5,5- dioxides containing per molecule atotal of from one to maximally seven chlorine atoms and are membersselected from among (a) dioxides as defined which are substituted in7-position by a radical of the formula wherein X represents --O-, S,SO--, or SO2 and R represents phenyl, chlorine-substituted phenyl,trifluoromethyl-phenyl, lower alkyl-phenyl, hydroxy-phenyl, loweralkoXy-phenyl or amino-phenyl,

and the 9-position of which is occupied by hydrogen or chlorine, and

(b) Dioxides as defined which are substituted in 9-position by phenoxyor chlorophenoxy, and the 7-position of which is occupied by hydrogen,

the 2- and -positions of which dioxides as defined under (a) and (b)supra are each occupied by hydrogen or chlorine,

the 3-position of which dioxides is occupied by hydrogen,

chlorine, nitro, or trifluoromethyl, and

the nitrogen atom in 6-position of which dioxides is occupied by oneequivalent of divalent calcium, manganese or zinc, are distinguishedparticularly from the corresponding free acids and the alkaline metalsalts, but also from other salts of divalent metals such as iron,strontium, barium, mercury, copper or cadmium by a very rapid inset offull insecticidal action against such noxious insects as the larvae ofColorado beetle and locusts, against which a rapid inset is of vitalimportance for the saving of the crops. Thus spraying with an aqueouscarrier containing only 0.1 g. per liter of the above mentioned zinc,calcium or manganese salt achieves a 100% killing of Leptinotarsa larvaewhile the sodium or potassium salt or the free7-(p-ch1orophenoxy)-10chloro-6H-dibenzo[c,e]-l,2-thiazine 5,5 dioxide applied in the sameconcentration, atfords a 100% kill only after 24 hours or later.

Another class of particularly active compounds according to theinvention, also falling under Formula I, comprises halogenated6H-dibenzo[c,e]-l,2-thiazine 5,5 dioxides of which dioxides,

the 1-position is occupied by hydrogen or chlorine,

the 2-position is occupied by hydrogen, chlorine, bromine,

or fluorine,

the 3-position is occupied by hydrogen, chlorine, bromine or nitro,

the 8-position is occupied by hydrogen, chlorine, trifiuoro methyl or,lower alkylthio,

each of the 7- and 9-positions is occupied by hydrogen,

halogen of an atom number ranging from 9 to 35, trifluoromethyl or aradical of the formula wherein X represents-Oor S, and

R represents lower alkyl, lower alkoxy-lower alkyl, hy-

droxy-lower alkyl or chloro-lower alkyl,

and the nitrogen atom in 6-position is substituted by lower alkyl, loweralkyl-substituted amino-lower alkyl, phenyl, lower alkyl-phenyl,halogenophenyl wherein halogen has an atomic number ranging from 9 to35, trifluoromethyl-phenyl, halogenobenzyl wherein halogen has an atomicnumber ranging from 9 to 35, and trifluoromethyl benzyl, or, in freeacid form, by hydrogen,

the said dioxides containing per molecule at least two and maximallyseven halogen atoms of an atomic number. ranging from.9 to 35, and, whenthe 6-position is 06- cupied by hydrogen, at least two but not more thanfour of the positions 1, 2, 3, 7, 8, 9 and 10 of said molecule areoccupied by hydrogen.

Those active ingredients falling under the general Formula I areparticularly active against larvae of moths, carpet and fur beetles,which are substituted in the cfused benzo radical by one radical of theformula Optional results in this respect are obtainedwith thosecompounds in which the R --X- substituent is in o-position to thenitrogen bond (7-position). Of this subclass of compounds falling underFormula I those which are further substituted by halogen, have proved tobe particularly active when they contain the halogen atom in ppositionto the nitrogen bond (9-position) in the c-fused benzo radical.

The new 6H-dibenzo[c,e]-l,2-thiazine,5,5-dioxides of the general FormulaI, which can also be termed substituted 2,2-diphenyl sultams, areproduced by a first process by diazotising a substituted Z-aminobenzenesulphonic acid anilide of the general Formula II HgN m 0 (RIX) n t Swherein R, R R R X, m, n, p and q have the meanings given above,decomposing the diazonium salt formed in the presence of a heavy metalcatalyst such as copper powder whereby a direct bond between the C atomin the o'position of the benzene sulphone radical and the C atom in theo-position of the aniline radical is formed. The diazotisation isperformed in the usual way, preferably in a mixture of glacial aceticacid and concentrated hydro chloric acid.

The diazonium salt is decomposed preferably in an acetic acid aqueous.solution, buifered for example, with sodium acetate, in the presence ofa copper powder as catalyst.

A second process for the production of 6H-dibenzo [c,e]-l,2-thiazine-5,5dioxides of the general Formula I consists in treating a substituted2-(o-aminophenyl)-benzene-l-sulphonic acid of the general Formula HIIIIH (III) wherein R, R R R X, m, n, p, and q have the meanings givenabove, or a halide, particularly the chloride, of such an acid withagents which split olf water or hydrogen halide.

Examples of agents which split off Water are: concentrated sulphuricacid, phosphorus pentachloride, phosphorus trichloride, phosphorusoxychloride, thionyl chloride etc. as well as mixtures thereof. Agentswhich split olf hydrogen halide are tertiary organic nitrogen bases suchas pyridine and dimethyl aniline and inorganic bases such as aqueoussodium hydroxide or sodium hydroxide suspended in organic solvents orsalts having a basic reaction such as alkali carbonates etc.

The reaction products obtained by both variations of the process whereinR is hydrogen can then be reacted in the presence of an acid bindingagent or after conversion into an alkali metal compound, with a reactiveester, particularly a halogen hydracid ester, of an alcohol of thegeneral formula R 'OH, wherein R has the meaning given above for R withthe exception of hydrogen or phenyl. Alkyl halides and dimethyl sulphateparticularly are mentioned as esters of such alcohols.

For the purpose of introducing halogen or to increase the halogencontent in the compounds produced as given above by the two variationsof the process, if desired these compounds, which already correspond toFormula I, can be reacted with chlorine or bromine until one or morechlorine or bromine atoms have entered the molecule as nuclearsubstituents. This subsequent halogenation can be performed in the usualway in the presence of suitable solvents and optionally adding acatalyst such as iron powder, iron chloride etc.

The starting materials of the general Formula H for the first processmentioned are obtained, insofar as they are not already known, bymethods known per se by reacting an o-nitrobenzene sulphonic acidchloride which may be substituted by halogen and/or trifluoromethyl withan aromatic amine which may be suitably substituted such as aniline,N-alkyl aniline, aminodiphenyl ether, diphenylamine etc., and reducingthe nitro group in the nitrobenzene sulphonic acid anilide formed to theamino group by known methods, e.g. with catalytically activated hydrogenor with iron according to Bchamp,

It is also possible to condense o aminobenzene sulphochloride or itsnuclear halogenated or nuclear trifluoromethylated derivatives vvith ananiline which may be substituted, e.g. in the presence of pyridine, toform the corresponding o-aminobenzene sulphonic acid anilides.

The following compounds, for example, are suitable starting materials ofthe general Formula II:

Z-aminobenzene sulphonic acid-4'-chloroanilide,

2-amino-3,S-dichlorobenzene sulphonic acid-4- chloroanilide,

Z-amino-3,5-dichlorobenzene sulphonic acid-3'- trifluoromethyl anilide,

2-amino-3,S-dichlorobenzene sulphonic acid-4'-chloro-3'- trifluoromethylanilide,

2-amino-5-chlorobenzene sulphonic acid-3',4-

dichloroanilide,

2-amino-5-chlorobenzene sulphonic -acid-5-chloro-2- (p-chlorophenoxy)-anilide,

2-amino-3,S-dichlorobenzene sulphonic acid-4',5'-dichloro-2'-(3,4"-dichlorophenoxy)-anilide,

2-amino-4,5-dichlorobenzene sulphonic acid-2'-ethoxy-4,5-dichloroanilide,

Z-amino-S-chlorobenzene sulphonic acid-N-methyl- 3',4'-dichloroanilide.

Starting materials (2 aminodiphenyl 2 sulphonic acids) of the generalFormula III are obtained, for example, by diazotising o-aminobenzenesulphonic acids which may be suitably further substituted and reactingthe diazonium salts with suitably substituted acetanilides in thepresence of copper powder and subsequently saponifying the acetylaminogroup. Also diphenyls which may be suitably substituted can be used asstarting materials. These are converted into the corresponding2-aminodiphenyl-2'- sulphonic acids by nitrating and sulphonating toform the corresponding 2-nitrodiphenyl-2'-sulphonic acids and reducingthe nitro group in the latter.

The following compounds, for example, are suitable starting material ofthe general Formula III:

2-aminodiphenyl-2-sulphonic acid,2-amino-3,5-dichloro-diphenyl-2'-sulphonic acid,2-amin0-4,4-dichloro-diphenyl-2-sulphonic acid,2-amino-4-bromo-diphenyl-2'-sulphonic acid,2-amino-4,5-dichloro-diphenyl-2-sulphonic acid,2-amino-5-chloro-3-phenoxy-diphenyl-2'-sulphonic acid,2-amino-5-chloro-3- (p-chlorophenoxy) -diphenyl-2- sulphonic acid,2-arnino-3-ethoxy-4,S-dichloro-diphenyl-2-sulphonic acid.

In the case where the starting material contains 1 or 2 nitro groups inthe e-ring, the reduction cannot be carried out according to the methodof Bchamp, nor with catalytically activated hydrogen, but must becarried out with sodium sulfide.

The following non-limitative examples further illustrate the productionof the new 6H-dibenzo[c,e]-l,2 thiazine-5,5-dioxides. Parts andpercentages are given therein by weight and the temperatures are indegrees Centigrade.

Example 1Pr0ducti0n 0 2,3,7,9,10-pentachlor0-6H-dibenz0[c,e]-1,2-thiazine-5,5-dioxide (a) 2-amz'n0-4,5-dichlorobenzenesulfonic acid 2,4,5'- trichloroanilide.-26 parts of2-amino-4,5-dichlorobenzene sulfonic acid chloride are gradually addedto a solution of 20 parts of 2,4,5-trichloroaniline and 16 parts ofpyridine in 200 parts of benzene. Care is taken, by cooling, that thetemperature does not rise above 10 C. On completion of the addition ofall the sulfonic acid chloride, the mixture is left to itself forseveral hours at 20 C. and then worked up as follows: the pyridine isremoved with dilute hydrochloric acid and the benzene solution is Washedneutral with water, dried and concentrated. The residue is dissolvedwith sodium hydroxide solution and the reaction product is againprecipitated with acid, filtered off under suction and recrystallizedfrom ethanol. It melts at 153-155 The same compound is obtained if2-nitro-4,5-dichlorobenzene sulfonic acid chloride is condensed in theusual way with 2,4,5-trichloroaniline and the nitro compound is reducedby one of the known methods, e.g. with iron and hydrochloric acidaccording to Bchamp.

(b) 2,3,7,9,10-pentachlor0-6H-dibenzo [c,f]1,2-thiazine-5,5-d10xide.4l.8 parts of 2-amino-4,5-dichloro benzenesulfonic acid-2',4',5'-trichloroanilide are dissolved in 400 parts ofglacial acetic acid, 25 parts by volume of concentrated hydrochloricacid are added and the whole is diazotized in the usual way, i.e. atabout 010, with a solution of 7 parts of sodium nitrite in 20 parts ofwater.

The resultant diazo solutions is then poured into a previously prepared40 warm solution of 200 parts of sodium acetate in 300 parts of water inwhich 10 parts of Cu powder are suspended. There is an immediateenergetic development of nitrogen; an immediate and thorough mixture isattained by intensive stirring. As the greasy compound whichprecipitates contains copper, a further 20 parts of Cu powder must beadded in portions during the reaction in order to maintain the reaction.When no more nitrogen is generated, the reaction mixture is madestrongly alkaline with sodium hydroxide solution. The hot solution isfiltered and the crude 2,3,7,9,l0-pentachloro- 6H-dibenz [c.e] [1,2]thiazine-5,5-dioxide is precipitated from the filtrate. It is filteredoff under suction and dried at C. in vacuo. The compound can be purifiedby recrystallisation from alcohol. In the pure state it melts at240-242.

Example 2Pr0ductz'0n of 6-methyl-7- (p-chlr0phen0xy)-9,10-dichloro-6H-dibenzo[c,e] [1,2 thiazine-5,5-di0xide (a)7-(p-chl0rophenoxy)10-chl0r0 6H dibenzo[c,e][1,2]thiazine-5,5-dioxide.42.5 parts of 4,4'4iichloro-2- [o-aminobenzenesulphonamido1-diphenyl ether are dissolved in 300 parts of glacialacetate acid, and 25 parts by volume of concentrated hydrochloric acidare added to the solution. The suspension of the hydrochloride formed isdiazotised at 0-10 with a solution of 7 parts of sodium nitrite in 20parts of water. The solution of the diazonium compound is clarified byfiltration and then poured into a 60 warm solution of 200 parts ofsodium acetate in 300 parts of water which contains 10 parts of Cupowder. On completion of the nitrogen development, the reaction mixtureis kept for some time at 60 and then made strongly alkaline with sodiumhydroxide solution and filtered. The 7-(p-chlorophenoxy)-10-chloro-6H-dibenzo[c,e] [1,2] thiazine-5,5-dioxide is precipitatedfrom the filtrate with hydrochloric acid. The precipitate is filteredoff and dried in vacuo at about 100. The substance is obtained in a pureform by recrystallisation from ethanol; it melts at l80-l82.

(b) 7-(p-chl0r0phen0xy)-9,10-dichl0r0 6H dibenzo [c,e][1,2]-lhiazine-5,5-dioxide.-39.2 parts of 7-(pchlorophenoxy)-l0-chloro6H dibenzo[c,e][l,2]thiazine-5,5dioxide are suspended in 250 parts ofglacial acetic acid and about 8 parts of chlorine are introduced at 30-35 The chlorination mixture is diluted with water and the product isfiltered off under suction. After drying in vacuo at 100 its meltingpoint is between 220-225". If it is recrystallised from ethanol, then apure compound is obtained which melts at 229-231" and which, on exactdetermination of the constitution is found to be7-(p-chlorophenoxy)-9,l0-dichloro 6H dibenzo[c,e] [l,2]thiazine-5,5dioxide.

dibenz0[c,e][1,2]thiazine-5,5-di0xide.42.6 parts of 7- (p-chlorophenoxy)-9,10-dichloro 6H dibenzo[c,e] [1,2] thiazine5,5-dioxide are dissolvedin 500 parts of 2 N sodium hydroxide solution. 20 parts of dimethylsulphate are added to this solution and the whole is stirred for severalhours at 70-80". At the end of this time, the N- methyl derivative whichhas precipitated is filtered oil under suction and dried at 100 invacuo. On recrystallisation from ethanol, the pure6-methyl-7-(pchlorophenoxy)-9,10-dichloro 6H dibenzo [c,e][1,2]thiazine- 5,5-dioxide is obtained.

The following compounds of general Formula I are also produced by themethods described in the above examples from equivalent amounts of thecorresponding starting materials:

Examples (3) Heptachloro-9-phenoxy 6H dibenzo[c,e][l,2]thiaazine-5,5-dioxide (mixture, formed by subsequent chlorination of9-phenoxy-6H-dibenz[c,e][1,2]thiazine- 5,5-dioxide at 60-70 C.),

(4) 7-phenoxy-10-chloro-6H-dibenzo[c,e][1,2]

thiazine-S,5-dioxide,

(5) 2,3,9-tricl1loro-6H-dibenzo [c,e] [1,2] thiazine- 5,5-dioxide,

(6) 2,3,8,9-tetrachloro-6H-dibenzo [c,e] [1,2]

thiaZine-5,5-dioxide,

(7) 2,3,8-trichloro-6H-dibenzo[c,e] [l,2]thiazine- 5,5-dioxide, (maincomponent of a chlorination mixture obtained by chlorination of2,3-dichloro-6H-dibenzo[c,e] [1,2]thiazine-5,5-dioxide) (8)2,3,9-trichloro-8-trifluoromethyl-6H-dibenzo [c,e] 1,2] thiazine-S ,5-dioxide,

(9) 2,3,8,9,10-pentachloro-6H-dibenzo[c,e] [1,2]

thiazine-5,5-dioxide,

(10) 6-methyl-2,3,9-trichloro-6H-dibenzo [c,e] [1,2]

thiazine-5,5-dioxide,

( 1 1) 6-rnethyl-2,3,8,9,10-pentachloro-6H-dibenzo [c,e] [1,2]thiazine-5,5-dioxide,

( l2) 7-(2',4,6'-trichlorophenoxy) -2,3,10-triclt1loro-v H-dibenzo [c,e]1,2] thiazine-S ,5 -dioxide,

(13) 7-(2',4',5'-trichlorophenoxy) -2,10-dichloro- 6H-dibenzo[c,e][1,2]thiazine-5 ,5 -dioxide,

( 14) 7- (p-chlorophenoxy) -2,3, 10-trichloro-6H- dibenzo [c,e] [1,2]thiazine-5,5-dioxide,

( 15) 7- (chlorophenoxy) -2, l0-dich1oro-6H-dibenzo [c,e] [1,2]thiazine-5,5-dioxide,

( l6) 2-chloro-8, IO-bis- (trifluoromethyl) -6H-dibenzo [c,e] [1,2]thiaZine-5,5-dioxide,

( 17) 2,3 ,9, 1 0-tetrachloro-7-methoxy-6H-dibenzo [c,e] 1,2] thiazine-S,5 -dioxide,

(18) 6-ethyl-2,3,9-trichloro-6H-dibenzo [c,e] [1,2]

thiazine-S ,5 -dioxide,

(19) 2,3,9,10-tetrachlo1'o-6H-dibenzo [c,e] [1,2]

thiazine-S ,5 -dioxide,

(20) 2,3,9, l0-tetrachloro-7- 3 ,4,-dichlorophenoxy 6H-dibenzo [c,e][1,2] thiaZine-5,5-dioxide,

(21) 2,3,9, 1 0-tetrachloro-7- 2,4,5 '-trichlorophenoxy) -6H-dibenzo[c,e] 1,2] thiazine-5,5-dioxide,

(22) 2,3-dichloro-9- 3,4'-dichlorophenoxy) -6H- dib enzo [c,e] 1,2]thiaZine-S ,5 -dioxide,

(23) 2, 3-dichloro-9- (p-chlorophenoxy -6H-dibenzo [c,e] [1,2]thiazine-5,5-dioxide,

(24) 6-methyl-7- (p-chloro-phenoxy) -10-chloro- 6H-dibenzo [c,e] 1,2]thiazine-S ,5 -dioxide,

(25) 9-methoxy-2,3-dichloro-6H-dibenzo [c,e] [1,2]

thiazine-S ,5 -dioxide,

(26) 9-methylthio-2, 3 -dichloro-6H-dibenzo [c,e] [1,2] thiaZine-S ,5-dioxide,

(27) 7-methoxyethoxy-1,2,3,9-tetrachloro-6H- dibenzo[c,e] 1,2]thiazine-5,5 -dioxide,

(28) 9-( B-chloroethyl-thio -2,3,4,7-tetrach1oro-6-methyl-6H-dibenzo[c,e] 1,2] thiazine-S ,5 dioxide,

(29) 9- (B-hydroxyethoxy) -2,3,4,7-tetrachloro-6- methyl-6H-dibenzo c,e]1,2] thiazine-S ,5 -dioxide,

(30) 7-phenylthio-9-chloro-6-isopropyl-6H-dibenzo [c,e] 1,2] thiazine-S,5 -dioxide,

(3 1) 7-(p-methylphenylthio -9-cl1loro-6-ethyl-6H dibenzo[c,e][1,2]thiazine-5,5 -dioxide,

(32) 7-(m-trifluorornethyl-p-chloro-phenoxy) -6H- dibenzo [c,e] 1,2]thiazine-S ,5 -dioxide,

(3 3) 2,3,9,10-tetrachloro-7-(pchloro-phenylthio)- 6H-dibenzo[c,e][1,2]thiazine-5,5-dioxide,

(34) 2-chloro-3-trifiuorometl1yl-7-(p-methoxyphenoxy) -6H-dibenzo [c,e]1,2] thiazine-S ,5 -dioxide,

(35 9- (p-nitro-phenoxy) -2,3 -dichloro-6H-dibenzo [c,e] [1,2]thiaZine-5,5-dioxide,

(3 6) 3-nitro-7,8,9-trichloro-6H-dibenzo [c,e] [1,2]

thiazine-S ,5 -dioxide,

(37 3-nitro-7- (p-chloro-phenoxy) -6H-dibenzo [c,e] 1,2] t-hiazine-S ,5-dioxide,

(38) 7 (p-amino-phenoxy) -2,3-dichloro-6H dibenz0[c,e] 1,2] thiazine-S,5 -dioxide,

(39) 7- (p-hydroxyphenoxy) -2-chloro-6H- [c,e] [1,2]

thiazine-S ,5 -dioxide,

(40) 7-(p-chlorophenylsulfonyl) -2,3,9-trichloro-6H- dibenzo [c,e] 1,2]thiazine-S ,5 -dioxide,

(41) 7- 3',4'-dimethyl-phenyl-sulfoxido -2,3-dichloro-6H-dibenzo [c,e][1,2] thiazine-5,5-dioxide,

(42) 6- p-bromo-phenyl) -2, 3-dibromo-6H-dibenzo [c,e] 1,2] thiazine-S,5 -dioxide,

(43) 6-phenyl7,9-dibromo-6H-dibenzo [c,e] [1,2]

thiazine-S ,5 -dioxide,

(44) 6- 3',4-dirnethyl-phenyl) -7,9-dichloro-6H- dibenzo c,e] 1,2]thiazine-S ,5 -dioxide,

(45 6'- (rn-trifluoromethyl-phenyl) -7,9-dichloro-6H- dibenzo[c,e] [1,2]thiazine-5,5-dioxide,

(46) 6-benzyl-9-phenoxy-2,-3-dichloro-6H-dibenz0 [c,e] 1,2]thiazine-5 ,5dioxide;

(47) 6-(p-methyl-benzyl) -7-(p-chloro-phenoxy)- 6H-dibenzo [c,e] 1,2]thiazine-S ,5 -dioxide, (48) 6- 3 ',4'-dichloro-benzyl) -7-(p-chlorophenylthio)-2,10-dichloro-6H-dibenzo[c,e] [1,2] thiazine-5,5-dioxide, I

(49) 6-(m-trifluoromethyl-p-chloro-benzyl)-6H- dibenzo[c,e][1,2]thiazine-5,5-dioxide,

(50) 6-acetyl-7- (p-chlorophenoxy) -9, 10-dichloro- 6H-dibenzo[c,e][1,2]thiazine-5,5-dioxide,

(5 1) 6-(2,4-dichloro-benzoyl)-7-(p-chlorophenoxy-9,10-dichloro-6H-dibenzo[c,e] [1,2]thiazine- 5,5-dioxide,

(5 2) 6-benzoyl-7- (p-chlorophenylthio) -9, l-dichloro- 6H-dibenzo [c,e]1,2] thiazine-S ,5 -dioxide,

( 3) 6- ('y-N,N-dimethylaminopropyl) -2,3,9, 1 0- tetrachloro-6H-dibenzoc,e] [1,2] thiazine- 5 ,5 -dioxide,

( 5 4) 6-(fl-methylamino-ethyl -2,3,9, l-0-tetrachloro 6I-I-dibenzo[c,e] 1,2] thiazine-S ,5 -dioxide,

(55 Heptachloro 7-phenoxy-6H-dibenzo [c,e] [1,2] thiazine-5,5-dioxide(mixture, formed by subsequent chlorination of 7-phenoxy-6H-dibenzo[c,e][1,2]thiazine-5, S-dioxide, at 60-70 C.

(5 6) 2,9-difiuoro-8-trifluoromethyl-6H-dibenzo [c,e] [1,2]

thiazine-5,5-dioxide.

Example 57 Example 2 is repeated but the strongly alkaline solutionobtained by adding sodium hydroxide solution after completion of thenitrogen development and standing of the reaction mixture for about 30minutes, is filtered and then concentrated in vacuo until the sodiumsalt of 7-(p-chlorophenoxy)-l0-chloro-6H-dibenzo[c,e] [1,2]thiazine 5,5dioxide precipitates. The salt is separated by filtration and purifiedby recrystallization from ethanol.

Example 58 Example 2 is repeated but the strongly alkaline solutionobtained by adding sodium hydroxide solution after completion of thenitrogen development and standing of the reaction mixture for about 30minutes, is filtered and saturated aqueous calcium chloride solution isadded thereto, whereupon the calcium salt of the formula precipitates.It is separated by filtration from the mother liquor and washed withcold water. It is very slightly soluble even in hot water and does notmelt up to 300.

Example 59 100 parts of 7-(p-chlorophenoxy)-10-chloro-6H-dibenzo[c,e][1,2]thiazine-5,5-dioxide are dissolved in an aqueous sodium hydroxidesolution produced by dissolving 10 parts of caustic soda in 3000 partsof water, with stirring and heating to 90. 10 parts of active carbon arethen stirred into the hot solution and stirring is continued for about 5minutes. The hot solution of the sodium salt of the startingdibenzothiazine-dioxide is then filtered through hyfio under suction,and a clear tea-colored filtrate is obtained to which 150 parts byvolume of ethanol are added while stirring, the latter being continueduntil the liquid has cooled to about 5 0. A solution prepared bydissolving 20 parts of CaCl .2H O in 50 parts of water is then added tothe 50 warm liquid with strong stirring. Precipitation of the calciumsalt of 7-(p-chlorophenoxy)-10-chloro-6H- dibenzo[c,e][l,2]thiazine-5,5-dioxide begins immediately. Crystallization isfacilitated by seeding with a few crystals of the calcium salt preparedin a previous run.

The reaction mixture is then cooled to room temperature (20 C.), thetan-colored crystals are separated by suction filtration, then groundwhile still Wet, to set free occluded mother liquor, the latter isremoved by suction filtration and the crystalline filter cake is thenwashed 10 thoroughly with cold water. The calcium salt is then dried ina vacuum drying chamber at 70 until the water content has been reducedto at least about 2% The manganese salt and the zinc salt of7-(p-chlorophenoxy) 10 chloro-6I-I-dibenzo[c,e] [1,2]thiazine-5,5-dioxide are prepared by repeating the above procedure but using insteadof 20 parts of calcium chloride an equivalent amount of anhydrousmanganese dichloride, MnCl or zinc chloride, respectively.

The compounds of the Formula I can be applied in various forms, e.g. asdusts, Wettable powders, emulsions or oil solutions. In combination withsynergists and auxiliaries having a similar action, such as substancesof DDT- type activity, olive oil, peanut oil, phosphoric acid estersetc., a wider spectrum of biological activities is attained.

The compounds according to the invention described hereinbefore, andparticularly those defined in connection with the substituent R 'X-, canbe used according to the usual methods for textile finishing. They haveafiinity to keratin material and are excellently suitable, therefore,for the protection of such materials from injury by insects, inparticular they are suitable for the wash and light fast moth proofingof such materials both in the raw as well as in the processed state, forexample of raw or processed sheeps wool as Well as other animal hairs,fells and furs. In addition to the wash and light fast moth proofing inthe dyebath, the compounds can also be used for the impregnation of Wooland woollen articles in dry cleaning processes, the materials thenbecoming equally excellently moth proofed.

In addition to their insecticidal action on the larvae of the clothesmoth, the compounds of the general Formula I possess such an action onthe fur and carpet beetle. The textiles treated in any way desired withthe compounds according to the invention such as woollen blankets,woollen carpets, woollen underwear, woollen clothes and knitted goods,are thus protected from the usual types of insects which are injuriousto keratin material.

The agents used for the protection of keratin materials from injury dueto insects should contain the active ingredients of Formula I in finelydistributed form. Thus, solutions, suspensions and emulsions of theactive ingredients are particularly suitable for use.

Insofar as the compounds contain a hydrogen atom in the sulfonamidegroup, i.e. when R is a hydrogen atom, in the form of their alkali metalsalts they generally have good water-solubility. They can be applied tothe keratin material direct from these aqueous solutions, either bydipping the material for a shorter or longer time in the alkali metalsalt solutions, or spraying them with the solutions, or by treating themin the solutions at a raised temperature as in dyeing processes.

Compounds having no dissociating hydrogen atom in the sulfonamide groupcan be drawn onto the material to be protected for example from theiraqueous suspensions or emulsions, advantageously at a raisedtemperature, or such suspensions or emulsions can be used for sprayingthe material.

Because of their improved solubility in organic solvents, thesecompounds are particularly well suited for application from non-aqueousmedia. Thus the materials to be protected can simply be impregnated withthese solutions, or, if a suitable solvent is chosen, the moth-prooffinishing can be combined with a dry-cleaning process.

Propylene glycol, methoxyethanol, ethoxyethanol and dirnethyl formamidehave been found to be particularly good organic solvents to whichdistributing agents, emulsifying agents such sulfonated ricinus oil,sulfite waste liquor and fatty alcohol sulfates are particularlysuitable for this aspect of the invention involving the protection ofkeratinous materials.

The following non-limitative examples describe the production of variousforms suitable for application in practice. The parts and percentagesare given therein by weight.

0.5 part of 7-(p-chlorophenoxy)-9,l0-dichloro-6H-dibenzo[c,e][1,2]thiazine-5,5-dioxide are dissolved in parts of 0.1 N sodiumhydroxide solution and a little ethanol. This solution is diluted with3000 parts of water and 100 parts of wool are treated in this liquor forminutes at 60. 5 parts of 10% acetic acid are added and the treatment at60 is continued for another hour. The wool is then rinsed in the usualway and dried. On being tested, the wool is found to be resistant toattack by moth larvae, fur and carpet beetle larvae.

EXAMPLE II The following process, for example, can be used for theapplication of 6-methy l-7-(p-chlorophenoxy)-9,l0- dichloro 6Hdibenzo[c,e] [1,2]thiazine 5,5 dioxide:

0.5 part of active ingredient are dissolved in 10 parts of dimethylformamide and the solution is poured into 3000 parts of water whichcontains about 1-2 parts of an emulsifying agent, e.g. sulfonatedricinus oil.

100 parts of wool are treated in this liquor for 30 minutes at the boil.After rinsing and drying, the wool is found to be moth-proofed.

Naturally, in the treatment baths in Examples I and H, other auxiliariesas well as dyestuffs can be added.

EXAMPLE III First a solution of 6-rnethyl-7-(p-chlorophenoxy)-9,10-dichloro-6H-dibenzo[c,e] [1,2]thiazine-5,5-dioxide in glycolmonomethyl ether is prepared. 10 parts by volume of this solution arediluted with 200 parts by volume of a solvent suitable for dry cleaning,e.g. a suitable benzine fraction (Diluan S). If desired, cleansingadditives can be added. The woollen articles are then treated in thiscleaning liquid in the usual way and then squeezed out to a content ofsolvent of about 100% of the weight of the wool. After drying, they arefound to be moth-proofed.

Baths of the same or analogous composition can also be used in ananalogous manner for the moth proofing of untreated articles or ofarticles which have been treated in any way or cleaned.

Similar mixtures can also be used for spraying or sprinkling on wool inany stage of processing.

The keratin textile materials treated with the compounds according tothe invention are tested as to their resistance to attack by pests bythe following standardized methods:

Moths: SNV leaflet (Swiss Association for Standardization) No. 95901,Carpet beetles, (Anthrenus): SNV leaflet No. 95902, Fur beetles,(Attagenus): AATCC (American Association of Textile Chemists &Colorists) Year Book 1952 p. 123 if.

EXAMPLE IV Spray:

(a) 2 parts of -methyl-7-(p-chlorophenoxy)-9,10-dichloro-6H-dibenzo[c,e] [1,2] thiazine-5,5-dioxide are dissolved in 10parts of xylene and 88 parts of petroleum.

(b) 2 parts of the above active compound and 3 parts of1,1-bis-(p-chlorophenyl) -2,2,2-trichloroethane are dis solved in 10parts of xylene or another auxiliary solvent and 85 parts of petroleum.

Both solutions are excellently suitable, for example, for combattinginsects by spraying in houses as well as in store rooms and slaughterhouses.

EXAMPLE V Dash-2 parts of 9-phenoxy-heptachloro-6H-dibenzene[c,e][1,2]thiazine-5,5 dioxide produced as described in Example 3 aremixed instantly by milling with 5 parts of Aerosil and 93 parts oftalcum. This dust can be used, for example, for combatting pestsparticularly on clothes, carpets and the like woolen articles in thehousehold or in the storage rooms.

12 EXAMPLE VI Strewing agent.2 parts of 6-methyl-7-(p-chlorophenoxy) 10chloro 6H dibenzene[c,e] [1,2]triazine-5,5- dioxide are mixed with 20parts of kaolin and 78 parts of talcum. This strewing agent is suitablefor all uses where a finely pulverised material is of the type describedin the preceding example unsuitable because of dust formation.

We claim:

1. A chlorinated 6H-dibenzo[c,e]-l,2-thiazine-5,5-dioxide containing permolecule a total of from one to maximally seven chlorine atoms and beinga member selected from (a) a dioxide as defined which is, substituted in7-position by a radical of the formula R '-X-- wherein X is a memberselected from the group consisting of O--, S, SO-, and -SO and R is amember selected from the group consisting of phenyl,chlorine-substituted phenyl, trifluoromethylphenyl, lower alkyl-phenyl,hydroxy-phenyl, lower alkoxy-phenyl and amino-phenyl,

(b) a dioxide as defined which is substituted in 9-p0sition by a memberselected from the group consisting of phenoxy, chlorophenoxy andnitrophenoxy, and

the 3-position of the said dioxide under (a) and (b) supra beingsubstituted by a member selected from the group consisting of hydrogen,chlorine, nitro, and trifluoromethyl, and

the nitrogen atom in the fi-positionin said dioxide under (a) and (b)supra being substituted by a member selected from the group consistingof lower alkyl, lower alkanoyl, benzyl, lower alkylbenzyl, chlorobenzyl,benzoyl chloro-benzoyl and hydrogen, and the alkali metal salt, alkalineearth metal salt, and ammonium salt thereof when the nitrogen atom inthe 6-position is substituted with hydrogen.

2. A chlorinated 6H-dibenzo[c,e]-1,2-thiazine-5,5-dioxide containing permolecule a total of from one to maximally seven chlorine atoms and beinga member selected from among (a) a dioxide as defined which issubstituted in 7-posi' tion by a radical of the formula R '-O and Rrepresents phenyl, chlorine-substituted phenyl, trifluoromethyl-phenyl,lower alkyl-phenyl, hydroxyphenyl, lower alkoxy-phenyl or amino-phenyl,and

(b) a dioxide as defined which is substituted in 9-position by phenoxyor chlorophenoxy, and the 7-position of which is occupied by hydrogen,

the 3-position of the said dioxide as defined under (a) and (b), supra,being occupied by hydrogen, chlorine, nitro, or trifluoromethyl, and

the nitrogen atom in 6-positi0n in said dioxide being substituted bylower alkyl, lower alkanoyl, benzyl, lower alkylbenzyl, chloro-benzyl,benzoyl or chlorobenzoyl, or in free acid form, by hydrogen.

3. A member selected from the group consisting of heptachlorinated9-phenoxy-6Hdibenzo[c,e]-1,2-thiazine- 5,5-dioxide and the 6-methy1atedderivative thereof.

4. A member selected from the group consisting of heptachlorinated7-phenoxy-6H-dibenzo [c,e] -1,2-thiazine- 5,5-dioxide and the6-methylated derivative thereof.

5. A chlorinated 6H-dibenzo[c,e]-l,2-thiazine-5,5-dioxide as defined inclaim 1, wherein R -O represents p-chloro-phenoxy, in 7-position, eachof the 9- and 10-positions are occupied by chlorine, and each of the 2-,3- and 6-positions are occupied by hydrogen.

6. A chlorinated 6H-dibenzo[c,e]-1,2-thiaZine-5,5-di0xide as defined inclaim 1, wherein R 'O- represents p-chloro-phenoxy, in 7-position, eachof the 9- and 10-positions are occupied by chlorine, and each of the 2-and 3-positions are occupied by hydrogen, and the 6-position is occupiedby methyl.

7. A chlorinated 6Hdibenzo[c,e]-1,2-thiazine-5,5-dioxide as defined inclaim 1, wherein R '-O- represents p-chloro-phenoxy, in 7-position, the10-position is occu- 13 pied by chlorine, and each of the 2-, 3-, 6- and9-p0sitions is occupied by hydrogen.

8. A chlorinated 6H-dibenzo[c,e]-1,2-thiazine-5,5-dioxide as defined inclaim 1, wherein R O represents p-chloro-phenoxy, in 7-position, the-position is occupied by chlorine, each of the 2-, 3- and 9-positions isoccupied by hydrogen, and the 6-position is occupied by methyl.

9. A chlorinated 6H-dibenzo[c,e]-l,2-thiazine-5,5-diox ide containingper molecule a total of from one to maximally seven chlorine atoms andbeing a member selected from among (a) a dioxide as defined which issubstituted in 7-position by a radical of the formula R '-O- and Rrepresents phenyl, chlorine-substituted phenyl, trifluoromethyl-phenyl,lower alkyl-phenyl, hydroxyphenyl, lower alkoxy-phenyl or amino-phenyl,

and the 9-position of which is occupied by hydrogen or chlorine, and

(b) a dioxide as defined which is substituted in 9-position by phenoxyor chlorophenoxy, and the 7-position of which is occupied by hydrogen,the 2- and 10-p0sitions 0f the dioxide as defined under (a) and (b)supra being each occupied by hydrogen or chlorine, the 3-position of thesaid dioxide being occupied by hydrogen, chlorine, nitro, ortrifluoromethyl, and the nitrogen atom in 6-position in said dioxidebeing substituted by an alkali metal or ammonium ion. 10. A chlorinated6H-dibenzo[c,e]-1,2-thiazine-5,5-dioxide containing per molecule a totalof from one to maximally seven chlorine atoms and being a memberselected from among (a) a dioxide as defined which is substituted in7-position by a radical of the formula R 'O and R represents phenyl,chlorine-substituted phenyl, trifiuoromethyl-phenyl, lower alkyl-phenyl,hydroxyphenyl, lower alkoxy-phenyl or amino-phenyl,

14 and the 9-position of which is occupied by hydrogen or chlorine, and(b) a dioxide as defined which is substituted in 9-position by phenoxyor chlorophenoxy, and the 7-position of which is occupied by hydrogen,the 2- and l0-p0sitions of the dioxide as defined under (a) and (b)supra being each occupied by hydrogen or chlorine. the 3-position of thesaid dioxide being occupied by hydrogen, chlorine, nitro, ortrifluoromethyl, and the nitrogen atom in 6-position in said dioxidebeing substituted by one equivalent of divalent metal ion. 11. Achlorinated 6H-dibenzo-[c,e]-1,2-thiazine-5,5-dioxide as defined inclaim 10, wherein said divalent metal is selected from among calcium,zinc and manganese.

12. A chlorinated 6H-dibenzo-[c,e]-1,2-thiazine-5,5-dioxide as definedin claim 10, wherein said divalent metal is calcium.

13. 7-(p-chlorophenoxy)-9,IO-dichloro 6H dibenzo- [c,e][1,2]thiaZine-5,5-dioxide.

14. 6-methyl-7-(p-chlorophenoxy) 9,10 dichloro-6I-I- dibenzo [c,e] [1,2]thiazine-5 ,5 -dioxide.

15. 7-(p chlorophenoxy) 10 chloro 6H dibenzo- [c,e][1,2]thiazine-5,5-dioxide.

16. 6-methyl-7-(p-chlorophenoxy) 10 chloro-6H-dibenzo c,e] 1,2]thiazine-S ,5 -dioxide.

References Cited UNITED STATES PATENTS 3,198,793 8/1965 Hilger et al.260-243 3,210,348 10/1965 Rey-Bellet et al. 260-243 WALTER A. MODANCE,Primary Examiner.

JOHN M. FORD, Assistant Examiner.

1. A CHLORINATED 6H-DIBENZO(C,E)-1,2-THIAZINE-5,5-DIOXIDE CONTAINING PERMOLECULE A TOTAL OF FROM ONE TO MAXIMALLY SEVEN CHLORINE ATOMS AND BEINGA MEMBER SELECTED FROM (A) A DIOXIDE AS DEFINED WHICH IS SUBSTITUTED IN7-POSITION BY A RADICAL OF THE FORMULA R1''-XWHEREIN X IS A MEMBERSELECTED FROM THE GROUP CONSISTING OF -O-, -S-, -SO-, AND -SO2-, ANDR1'' IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF PHENYL,CHLORINE-SUBSTITUTED PHENYL, TRIFLUOROMETHYLPHENYL, LOWER ALKYL-PHENYL,HYDROXY-JPHENYL, LOWER ALKOXY-PHENYL AND AMINO-PHENYL, (B) A DIOXIDE ASDEFINED WHICH IS SUBSTITUTED IN 9-POSITION BY A MEMBER SELECTED FROM THEGROUP CONSISTING OF PHENOXY, CHLOROPHENOXY AND NITROPHENOXY, AND THE3-POSITION OF THE SAID DIOXIDE UNDER (A) AND (B) SUPRA BEING SUBSTITUTEDBY A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CHLORINE,NITRO, AND TRIFLUOROMETHYL, AND THE NITROGEN ATOM IN THE 6-POSITION INSAID DIOXIDE UNDER (A) AND (B) SUPRA BEING SUBSTITUTED BY A MEMBERSELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL, LOWER ALKANOYL,BENZYL, LOWER ALKYLBENZYL, CHLOROBENZYL, BENZOYL CHLORO-BENZOYL ANDHYDROGEN, AND THE ALKALI METAL SALT, ALKALINE EARTH METAL SALT, ANDAMMONIUM SALT THEREOF WHEN THE NITROGEN ATOM ON THE 6-POSITION ISSUBSTITUTED WITH HYDROGEN.